JPH04172444A - Silver halide photosensitive material for color photography - Google Patents

Abstract

PURPOSE:To prevent damage resistance and color image stability from being deteriorated and also restrain contamination by a processing liquid and a rise in the minimum image density by putting a non-sensitized atomized silver halide emulsion, a polymer having hydroquinone skeleton, and an ultraviolet absorber in a protecting layer. CONSTITUTION:A non-sensitized atomized silver halide emulsion and/or an atomized silver halide emulsion having the surface and/or inside of its particles covered are contained in a protecting layer or hydrophilic colloid and a polymer or coplymer having cyclic units including hydroquinone skeleton and an ultraviolet absorber are also contained in the protecting layer. The polymer or copolymer having cyclic units including hydroquinone skeleton is preferably a compound expressed by the formular I or II. The effect of restraining a rise in D min using the atomized emulsion in the protecting layer and a coupler in a sensitized emulsion layer adjacent the protecting layer is remarkable when the coupler shows high activity.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material whose photographic performance does not change much with respect to changes in processing liquid composition. (Prior Art) In recent years, demands on the photographic performance of silver halide color photographic materials have become increasingly strict. It is desirable that the composition of the developing solution is always controlled to be constant, but in reality, the composition of the developing solution varies between laboratories or even from day to day even within the same laboratory. For example, concentration due to water evaporation, oxidation of the developing agent due to oxygen, differences in the processing ratio of sensitive materials with different halogen compositions, incompatibility in replenishment amounts, pH decrease due to absorption of carbon dioxide in the air, etc. There are a wide variety of factors contributing to the fluctuation of There is a strong desire for a silver halide color light-sensitive material that always exhibits constant photographic performance despite these changes in composition after development. For this reason, many studies have been conducted to date. For example, a patent for preventing the release of iodine ions and development inhibitors and improving processing solution contamination by containing a fine-grained silver halide emulsion in the protective layer is patented in France, for example. Patent 912,60
No. 5, U.S. Patent No. 3,892°572, U.S. Patent No. 3,9
No. 61,963, etc., and it is disclosed in US Pat. No. 3,737, etc. that a deposited layer containing colloidal silver is separately provided to prevent the fine grain silver halide emulsion in the protective layer from eluting into the processing solution. No. 317. In addition, by containing a fine-grain silver halide emulsion in the protective layer,
U.S. Patent No. 4,77 discloses that it is possible to prevent the magnitude of interimage effect caused by mercapto-1,3,4-thiadiazol compound from changing depending on the iodide ion concentration in the processing solution.
No. 2,546. On the other hand, efforts have been made to improve sharpness by thinning the layer, reducing light scattering due to the shape of silver halide grains, and improving the edge effect. Methods for thinning the layer include reducing the amount of silver halide emulsion and coupler using a highly active coupler, reducing the amount of silver halide emulsion using a 2-equivalent coupler, reducing the amount of high boiling point organic solvent, and increasing the thickness of the intermediate layer using a highly active color mixing inhibitor. Various methods were adopted, including reduction. When the coupler in the light-sensitive silver halide emulsion layer (in the case of a photographic material, the blue-sensitive emulsion layer) adjacent to the protective layer is made highly active, layer thickness can be reduced as expected. , when the protective layer contains a fine-grain silver halide emulsion in order to stabilize the photographic performance against fluctuations in the composition of the processing solution,
This results in an increase in the minimum image density (Dmin). Particularly in the case of color reversal photographic materials, the fine-grain silver halide emulsion in the i-layer is not fully developed in the first development (black and white development), but is developed in a color developer, and the oxidized form of the developing agent is It is thought that the oxidized form of the developing agent diffuses into the highly active coupler-containing photosensitive emulsion layer adjacent to the protective layer, undergoes a coupling reaction with the highly active coupler, and increases Dmin. Therefore, it is considered that at least one protective layer contains a hydroquinone derivative, which is a scavenger of the oxidized product of the developing drug, to suppress the increase in Dmin. It has long been known to use various substituted hydroquinones as scavengers for the oxidized developing agent. For example, regarding the use of monolinear alkylhydroquinone, US Pat.
-106329, etc., and U.S. Pat. No. 3,700,
No. 453, West German Patent Publication No. 2,149,789, and Japanese Patent Application Laid-open Nos. 50-156438 and 49-106329. On the other hand, regarding dilinear alkylhydroquinone, US Pat. Nos. 2,728,657 and 2,732.
300, British Patent No. 752,146, 1.806,
No. 208 and ``Chemical Abstracts'' magazine, volume 58, 63
67h, etc., and for di-branched alkylhydroquinone, U.S. Pat.
No. 300, British Patent 1. ．． No. 086,208, above-mentioned "Chemical Abstracts" magazine, JP-A-15643-1986
No. 8, JP-A-50-2124.9, JP-A No. 56-4081
There is a description in issue 8 etc. In addition, regarding the use of alkylhydroquinone as a color stain prevention agent, British Patent No. 558゜258, British Patent No. 5
57,750 (corresponding U.S. patents 2.360.290, 557.802, 731.301 (corresponding U.S. patents 2.701..197), U.S. patent 2.336
, No. 327, No. 2゜403.721, No. 3,582,
No. 333, West German Patent Publication No. 2,505,061 (corresponding to JP-A-50-110337), Japanese Patent Publication No. 56-40816
There is also a mention in the issue. (Problems to be Solved by the Invention) However, according to research by the present inventors, the use of the above-mentioned substituted hydroquinone significantly deteriorates scratch resistance. That is, if an undeveloped photosensitive material is inadvertently scratched with a sharp object, the scratches will be noticeable even after the development process. In addition, when developing this photosensitive material, even if the processing solution is replenished according to the amount of processing, if a large amount of processing is performed, such as 50 or more in 135 size, the color density of the photosensitive emulsion layer, especially near the protective layer, will decrease. There is a tendency to This is thought to be caused by substances (e.g. iodide) eluted from the photosensitive material into the processing solution.If a substance that changes photographic performance is eluted from the photosensitive material even after replenishing an appropriate amount of processing solution, this This is generally referred to as processing liquid contamination. Further, according to the research of the present inventor, at least one of the protective layers
The layer contains an ultraviolet absorber, and at least one of the protective layers
When the layer contains the above-mentioned substituted hydroquinone, a serious problem arises in that the color image after the photosensitive material is developed is easily faded by light. Therefore, an object of the present invention is to use a relatively highly active coupler in the light-sensitive emulsion layer adjacent to the protective layer, and to suppress fluctuations in photographic performance due to fluctuations in the processing solution composition by using a non-light-sensitive fine-grain silver halide emulsion. The object of the present invention is to provide a color photographic material having a sufficiently low Dmin without deteriorating the scratch resistance and color image stability or contaminating the processing solution by including the compound in at least one protective layer. (Means for Solving the Problems) The above object of the present invention is to have at least two photosensitive silver halide emulsion layers on a support, and to In a silver halide color photographic light-sensitive material having at least one hydrophilic colloid layer (protective layer) on the side far from the support, the at least one protective layer contains a non-light-sensitive fine grain silver halide emulsion and/or grains. Contains a fine grain silver halide emulsion whose surface and/or the inside of the grains are fogged, and at least one protective layer contains at least one polymer or copolymer having a repeating unit containing a hydroquinone skeleton, The present invention has been achieved using a silver halide color photographic material characterized in that at least one protective layer contains at least one type of ultraviolet absorber. The polymer or copolymer having a repeating unit containing a hydroquinone skeleton of the present invention is disclosed in US Pat.
No. 8, JP-A-57-17949, JP-A No. 61-16984
No. 4, etc., but it should not be used in combination with non-photosensitive fine-grain silver halide emulsions, etc., and should not be used in combination with a non-photosensitive fine grain silver halide emulsion, etc., and should not be used in combination with a There is no disclosure of suppressing the increase in D win due to the fine grain emulsion and the highly active coupler in the emulsion layer adjacent to the protective layer.Usually, in color photographic materials, at least one of the protective layers is
An ultraviolet absorber is used in the layer to prevent static in the undeveloped photosensitive material and to improve color image stability against light in the developed photosensitive material. The present inventor has discovered that this ultraviolet absorber decomposes when low molecular weight substituted hydroquinone is present in its vicinity, resulting in poor color image stability due to light. For polymers,
For some reason, it is assumed that because the ultraviolet absorber is not decomposed, the color image stability due to light does not deteriorate. Furthermore, while low molecular weight substituted hydroquinone contaminates the processing solution, the reason why the polymer or copolymer having a repeating unit containing a hydroquinone skeleton of the present invention does not contaminate the processing solution is due to the difference in molecular weight. This is thought to be due to the very different diffusivity. Furthermore, compared to low molecular weight substituted hydroquinones, the polymers or copolymers of the present invention having repeating units containing hydroquinone skeletons are superior in scratch resistance. The polymer or copolymer having a repeating unit containing a hydroquinone skeleton of the present invention is preferably a compound represented by the following general formula (1) or general formula (II). R1 I-1 where R1 is represents a hydrogen atom, a halogen atom, an alkyl group, and R2, R3, it', It5, R6 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, Amide group, sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group,
1. INK', L, and INKz represent a single bond or a divalent linked group. Formulas (I) and (11) will be explained in more detail. In the formula, +t
'a represents a water atom, a halogen v atom (α, El r, FγC, etc.), an alkyl group (t# purple number/~t, M is methyl, )゛thyl), It2. R3,it', R5,
Hydrogen atoms, halogen atoms (cl!, Br, R7
:c), alkyl group (number of carbon atoms/~-θ; examples include methyl, t-butyl, octyl, 5ec-dodecyl, and -hantadecyl), alkoxy MIR1ddi~20° e.g. methoxy, butquine, octyloxy), alkylthio group (number of carbon atoms/~20, e.g. methylthio, hexylthio, dodecylthio 1), acyl group (number of carbon atoms λ~20゜example!
- is acetyl, prohanoyl, butanoyl), sulfonyl group (charcoal EI5 (/~coOe example t [butanesulfonyl,
benzenesulfonyl), alkoxycarbonyl group (carbon number λ to coθ. Njtf methoxycarinyl, ethoxycarbonyl),
7 Mido group (carbon number 2 to θ; for example, acetylamine, be/diylamine/, hexane 7 mido 2, sulfonamide &
(charcoal &ri/~Jo, e.g. methanesulfone 7mi)-,
p-toluenesulfonamide). Alkoxycarbonylamino! (Carbon el-2~20
゜For example, methoxycarbonylamino), +7+zite group (carbon number l-co0, e.g. car-2moylamino. carbamoyl), and R and It may jointly form a carbon ring. L, INKI, L
, INK2 has a single bond or a divalent linking group

[Carbon number 0-
JQ, Example ttl-CONH-1-s I'L'rz
When it is a hydrogen atom or an alkyl group, it is preferable, and R2,
Tt3, R', 15. R6 is a hydrogen atom, an alkyl group,
Preferably, it is an alkoxy group or an alkoxy group.
, LINK', LINK2 may be divalent linked groups.
preferable. The general formula (1
) Also, the makuragaeshi unit of the general formula (11)
co-polymerization with other ethylenically unsaturated monomers that can undergo addition polymerization with
It is a combination of moss. If kept together with other single species, Akuri
alkyl acid, α-chloroacrylic acid, α-alkyl acrylic acid (metallic acid)
Bird-proofed from acrylic fRs such as tacrylic acid (TC, etc.)
esters or amides (e.g. t-butyl acrylic)
amide, methyl acrylate, methyl methacrylate,
Ethyl acrylate, low propyl acrylate. n-butyl acrylate, n-butyl methacrylate
, -monoethylhexyl acrylate, rhohexyl acrylate
rylate, octyl methacrylate), vinyl ester
Steles (e.g. vinyl acetate, acrylonitrile)
], aromatic vinyl compounds (e.g. styrene, vinyl
lutoluene, divinylbenzene, etc.], vinyl alkyl
Ethers (4SL vinyl ethyl ether, maleic
acid esters, etc.). The average molecular weight of the polymer according to formula (f) is /, 000 ~ /θ
01θ0θ, preferably 2°000 to 10
, 0θθ. The average molecular weight of the polymer according to formula (n) is jOθ~10. θ
00, preferably /, 00o-s, ooθ
It is. For the synthesis of polymers according to formula (I), US Pat.
t, No. 021, Japanese Patent Publication No. 1997-17-7, No. 7 Rihiro. The method described in JP-A No. 7/-/i<ri, r≠≠ or its
γC can be performed by a method similar to this. JP-A-1-204 for the combination of polymers according to formula (11) +iI
337 by the method of Kigeki or a method similar thereto.
can become. Specific examples of the polymer used in the present invention are shown below.
The invention is not limited to these. H3 0F1x: y = 6! : 4. jx:y=3
0:! ;0 Li x:y-=7.2:jf+51
CⅡJ Y r:r nox:y=rj:/j Contains a repeating unit containing a hydroquinone skeleton of the present invention
The homopolymer or copolymer is preferably dispersed in water.
In the form of so-called polymer latex, coating liquid (many types
gelatin solution) and applied. In the present invention, the polymeric color stain inhibitor is introduced into the protective layer.
It is used to introduce the coupler into the emulsion layer.
Any known method can be applied. For example, Futar
Acid alkyl esters (dibutyl phthalate, dioctyl
phthalates, etc.), phosphate esters (diphenylphos),
Phate, triphenyl phosphate, tricresyl
phosphate, dioctyl butyl phosphate),
Citrate esters (e.g. acetyl tributyl citrate)
), benzoic acid esters (e.g. octyl benzoate),
Lucylamide (e.g. diethyl laurylamide), fat
Acid esters (e.g. dibutoxyethyl succinate,
Dioctyl azelate 9, trimesic acid ester (e.g.
tributyl trimesate), or boiling point approximately 30°C
organic solvents such as ethyl acetate, butyl acetate,
Lower alkyl acetate such as chill, ethyl propionate
, secondary butyl alcohol, methyl isobutyl ketone,
β-ethoxyethyl acetate, methyl cellosolve acetate
After dissolving in tate etc., it is dispersed in a hydrophilic colloid. Mix the above-mentioned high boiling point organic solvent and low boiling point organic solvent.
You can stay there. Having a repeating unit containing the hydroquinone skeleton of the present invention
Polymers or copolymers contain fine halogen particles in the protective layer.
The amount of silver emulsion, halogen composition, grain size, etc., and storage
The thickness of the protective layer and the activity of the coupler in the adjacent light-sensitive emulsion layer
In the protective layer, 1 x l O-'
~1 x 10-'L, /rd is preferably contained.
The content of
is particularly preferred. In the present invention, the fine grain emulsion in the protective layer and the fine grain emulsion adjacent to the protective layer are
on D sin due to the coupler in the adjacent light-sensitive emulsion layer.
The effect of suppressing elevation by the polymeric hydroquinone is as follows:
The coupler in the adjacent photosensitive emulsion layer is highly active.
This is noticeable in some cases. For example, the photosensitive silver halide emulsion layer is a blue-sensitive emulsion layer.
, the yellow coupler is JP-A-63-1004
When the compound represented by the general formula (I) described in No. 56,
The effects of the present invention are remarkable. In addition, in the present invention, the following ultraviolet absorbers are used as the above-mentioned ultraviolet absorber.
The compounds represented by the general formulas (m) to (V) alone or
It is particularly preferable to use them in combination. General formula (m) (In the formula, R"+, Ro2, R°3, Ro4, R's are
Hydrogen, halogen atom, alkyl group, cycloalkyl, respectively
group, alkoxy group, acyl group, aryl group, aryl
Oxy group, alkoxycarbonyl group, alkenyl group,
Represents a tro group or a hydroxy group. ) General formula (TV) (In the formula, R°6, Ro7, Ro8, and Ro9 each represent water.
element, halogen atom, nitro group, hydroxyl group, alkyl
group, alkoxy group, aryl group or aryloxy group
and Xo represents -〇〇- or -CO〇-
, ) General formula (V)
Kyl group, aryl group, alkoxy group, aryloxy group
, alkylthio group, arylthio group, amino group, hydro
xy group, cyano group, nitro group, carbamoyl group, sulfo group
Nyl group, sulfamoyl group, sulfonamide group, acyl group
It is an oxy group or an oxycarbonyl group, and R°3. is water
or an alkyl group, and Ro16 and Ro, 7 are
Ano group, -COOR'. , -CONHR', , -C
OR', , -3o□R', and R'll+ is a
Represents an alkyl group or an aryl group. General formula (Vl) R21 and R8° may be the same or different and are hydrogen atoms,
represents an aliphatic group or an aromatic group, provided that R26 and Rig
cannot be a hydrogen atom at the same time. ), R2H and R
84 may be the same or different; cyano group, carbamoyl
group, sulfamoyl group, formyl group, -COR1,,
-5OR, , -SOsRmy, -SO*0Rzt, ma
or -COOR,. Here, aliphatic group refers to substituted or unsubstituted straight chain, branched
Indicates a chain or cyclic alkyl group, and is substituted with an aromatic group.
or an unsubstituted monocyclic or condensed benzene ring.
indicates a group. Such UV absorbers are added to the layer in which this compound is added.
Contains about 0.01 to 2 parts by weight per 1 part by weight of binder.
Preferably. By the way, the amount of binder applied in the photographic layer is usually 0.1~
It is about 3 g/d. Below, general formulas (I[[), (IV), (V) and (VI
), specific examples of ultraviolet absorbers represented by
The invention is not limited to these. (UV absorber compound example) CHs III-110H CHI CHx COOCs H+F II-16 ■-20 H3 ■-23 1] ■-1 v-2 V-3 H0 0CI 2 Hz s V-5 HO ■-6 0H0 V-7 H0 CHs ■-10 C,H5 Vl-3 Vl-4 C-OC00CR3 (weight ratio) ■-5 x/y = 7/3 Details of the ultraviolet absorber represented by general formula (II+) are as follows:
Special Publication No. 42-26187, No. 48-5496, No. 4
g-41572, U.S. Pat. No. 3,754.919,
No. 4,220,711, etc. General formula (r
Details of the benzophenone ultraviolet absorber represented by V)
No. 48-30493 (U.S. Pat. No. 3,698.
No. 907) and No. 4g-31255, etc.
. For details of the ultraviolet absorber represented by general formula (V), please refer to JP-A
No. 47-10537, No. 5B-111942, and the United States
It is described in Patent No. 3,707,375 and the like. general formula
Details of the ultraviolet absorber represented by (Vl) can be found in the U.S. patent
No. 4,045,229. These ultraviolet absorber layers are combined with silver halide emulsion layers and/or silver halide emulsion layers.
or other photographic layers, conventionally known
It depends on the method. That is, typically a boiling point of about 175
A high boiling point organic solvent above ℃ (along with a low boiling point solvent if necessary)
(used) or a low boiling point solvent (dissolved in gelatin aqueous solution)
Using a surfactant in a hydrophilic binder such as
This dispersion is added to the desired hydrophilic colloid layer.
Just add it. The high boiling point organic solvent used in the present invention contains the ultraviolet absorber.
Remove volatile organic solvents and amphipathic solutes from the organic layer with
The relative refractive index of the hydrophilic layer forming the non-photosensitive layer
0.9875 to 1 for polymer thin film, Q125 (7)
Range Thea 6J: '+i, m selected, boiling point 175°C or higher
Any organic solvent with a high boiling point above may be used, but preferably
, a non-volatile material whose own refractive index is less than 1.48g
organic solvent, more preferably an alkyl phosphate ester
, citric acid ester, fatty acid ester, carbonic acid ester
, amides, esters and ethers of fluorine-containing alcohols
It is. In the ultraviolet absorber-containing layer of the present invention, US Pat.
, No. 363, West German Patent Application (OLS) No. 2.541
, No. 274 and No. 2,541,230, etc.
Polymerized dispersions of acrylic esters, etc.
Can be added. These UV absorbers can be used alone or in combination of two or more.
You can. The amount of ultraviolet absorber used in the present invention may be one or two types.
The total amount of species or more is lXl0-' mol to 8x10-3 mol
/i, preferably 2X10'' mole to 5XIO-' mole
/ Go. The number of protective layers in the present invention is one or more, particularly 2 to 4 layers.
Layers are preferred. At least one layer of the protective layer of the present invention contains a non-photosensitive fine particle halo.
Silver germide emulsion and/or grain surface and/or
or a fine-grain silver halide emulsion with fogging inside the grains.
containing a hydroquinone skeleton in at least one of the protective layers.
of a polymer or copolymer having a repeating unit containing
Contains at least one type and has at least one layer of protection
The layer contains at least one type of ultraviolet absorber. protective layer
If there are two or more layers, non-light-sensitive fine-grain silver halide emulsions may be used.
and/or particle surface and/or particle interior.
The fine-grain silver halide emulsion covered with
Contained in the furthest protective layer or the adjacent protective layer
Preferably. Polymers with repeating units containing a hydroquinone skeleton also
Alternatively, the copolymer may be used in the above fine-grain silver halide emulsion-containing layer.
or at least one protective layer closer to the support.
Preferably, it is contained in UV absorbers protect all but the protective layer furthest from the support.
It is preferably contained in the layer and contains a hydroquinone skeleton.
In a layer containing a polymer or copolymer having repeating units.
Most preferably, it is contained. At least one of the protective layers of the invention preferably has a support
The protective layer located furthest from the body is soluble in the processing solution.
and/or an insoluble matting agent.
stomach. The dry film thickness of each protective layer of the present invention is 0.2 μm to 6 μm.
It is preferably 0.4 μm to 4 μm.
It is particularly preferable. In addition, the total thickness of the protective layer of the present invention is
, preferably 0.8 μm to 8 μm, and 1.0 μm
It is particularly preferable that the thickness is from m to 6 μm. The protective layer of the present invention is two or more layers, and at least one layer
When containing oil droplets, the outermost layer of the plurality of protective layers
The density of oil droplets in the plurality of protective layers is
It is preferable not to make it the maximum. Non-photosensitive fine grain silver halide emulsion and/or of the present invention
or cover the particle surface and/or the inside of the particle.
In the protective layer containing a fine-grain silver halide emulsion,
Contains colloidal silver as described in No. 62-240963
Good too. Preferred embodiments of the present invention are shown below, but are limited to the following:
It is not something that will be done. For multiple protective layers, the first protective layer starts from the one closest to the support.
, a second protective layer, and a third protective layer. 1. The first protective layer may be a polymer having a repeating unit containing a hydroquinone skeleton.
A copolymer emulsified gelatin dispersion and a UV absorber.
Contains emulsified gelatin dispersion. 2nd protective layer non-photosensitive fine grain silver iodobromide emulsion, yellow colloidal silver, development treatment
Matting agents soluble and insoluble in liquids, static
Contains anti-stick agent. 2. First protective layer A polymer having a repeating unit containing a hydroquinone skeleton
or a copolymer emulsified gelatin dispersion and a UV absorber.
Contains emulsified gelatin dispersion. The second protective layer is a non-photosensitive fine-grain silver iodobromide emulsion containing yellow colloidal silver. A soluble matting agent, an insoluble matting agent and
Contains anti-static agent. 3. First protective layer A polymer having a repeating unit containing a hydroquinone skeleton
or copolymer emulsified gelatin dispersion. 2nd protective layer Emulsified gelatin dispersion of ultraviolet absorber, non-photosensitive fine particle oxide
Contains silver bromide emulsion and black colloidal silver. A soluble matting agent, an insoluble matting agent and
Contains anti-static agent. 4. First protective layer A polymer having a repeating unit containing a hydroquinone skeleton
or copolymer emulsified gelatin dispersion. The second protective layer contains an emulsified gelatin dispersion of ultraviolet absorber and a polymer latte.
Contains cous dispersion. Fine-grain silver halide emulsion covered with third protective layer grain surface, development
Matting agents that are soluble in the processing solution, matting agents that are insoluble, and stains.
Contains anti-tic agents. 5. First protective layer UV absorber emulsified gelatin dispersion and polymer latex
Contains a gas dispersion. 2nd protective layer A polymer with repeating units containing a hydroquinone skeleton
or emulsified gelatin dispersion of copolymer and particle surface.
Contains suspended fine grain silver halide emulsion. A soluble matting agent, an insoluble matting agent and
Contains anti-static agent. Substantially light-insensitive silver halide emulsions are primarily characterized by grain shape.
After the production, by not carrying out chemical ripening, or if necessary,
It is prepared by adding a desensitizer to the emulsion. Second, the silver halide grains have a surface or internal structure.
You can also use one covered with. Silver halide emulsion with fogging on the surface or inside of grains
is uniformly applied to both unexposed and exposed areas of photographic material.
A silver halide emulsion that can be developed. Silver halide emulsion with fogged inside of grains applied here
is a silver halide inner core with a fogged surface and its
A core shell consisting of an outer film of silver halide covering the surface.
This is an emulsion consisting of silver halide grains. The surface-fogged silver halide emulsion forms a surface latent image.
The resulting emulsion is treated with a reducing agent under appropriate conditions of pH, pA, and g.
or by heating under low p and Ag conditions.
or by applying negative exposure.
Can be prepared. As a reducing agent, stannous chloride, hydrazide
compounds such as ethanolamine, thiourea dioxide, etc.
Can be used. The internally covered silver halide grains cover the above surface.
Silver halide is deposited on the surface of suspended silver halide grains.
It is prepared by stacking to form an outer membrane. The thickness of the shell is the silver halide coated with the above surface.
The halo of the shell to be deposited depends on the particle size of the particles.
It can be adjusted by the amount of silver genenide. The amount of the silver halide emulsion is preferably 0.01 g to Ig/rrr.
Particularly preferred is 0.03 g/d to 0.5 g/d. Also, the grain size of the silver halide emulsion contained in this protective layer is
The size is preferably 0.03 to 0.5μ, and preferably 0.05 to 0.
3μ is particularly preferred. In the present invention, the protective layer is at least one layer, preferably
consists of 2-3 layers. The binder used in the protective layer or
Gelatin is preferred as the protective colloid, but other parent
Water-based polymers can also be used. Colloidal silver can also be added to the above protective layer.
Ru. The colloidal silver contained in the above protective layer is generally yellow.
Even yellow colloidal silver, which is used for filters, is
Blue, cyan or blue color used for antihalation layer
may be black colloidal silver. Also magenta or brown
Colored colloidal silver may also be used. Preferably blue, cyan
, black, magenta or brown colloidal silver. The coating amount of these colloidal silvers is o,oooi~0.1
g/rr? is desirable, especially 0.0005 to 0.05g
/I is preferable. The light-sensitive material of the present invention has a blue-sensitizing layer on a support, a green-sensitizing layer, and a green-sensitizing layer on a support.
layer, at least one silver halide emulsion layer of the red-sensitive layer
It is sufficient if the silver halide emulsion layer and the non-silver halide emulsion layer are
There are no particular restrictions on the number and order of photosensitive layers; typical
For example, on a support, the color sensitivity is substantially the same.
consists of multiple silver halide emulsion layers with different sensitivities.
Silver halide photographic material having at least one photosensitive layer
The photosensitive layer is sensitive to blue light, green light, and red light.
It is a unit photosensitive layer that has color sensitivity in either of the
In silver halide color photographic materials, the unit is generally
The arrangement of the photosensitive layers is a red-sensitive layer and a green-sensitive layer in order from the support side.
The chromatic layer and the blue-sensitive layer are installed in this order. However, depending on the purpose
Even if the above-mentioned installation order is reversed, the same color-sensitive layer
The order of placement may be such that different photosensitive layers are sandwiched between them. Between the above silver halide photosensitive layers and the top and bottom layers
A non-photosensitive layer, such as an intermediate layer between each coating, may be provided. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
No. 037, as described in the specification of No. 61-20038.
May contain una coupler, DIR compound, etc.
It may also contain a commonly used color mixing inhibitor. The multiple silver halide emulsion layers constituting each unit photosensitive layer are
, West Unique Ff No. 1.121.470 or British Patent
a high-speed emulsion layer as described in No. 923,045;
A two-layer structure of low-speed emulsion layers can be preferably used.
0Usually, the intensity of light gradually decreases toward the support.
It is preferable that the halogen emulsion layers be aligned, and between each halogen emulsion layer
A non-photosensitive layer may be provided.
-112751, 62-200350, 62-
Described in No. 206541, No. 62-206543, etc.
There is a low-speed emulsion layer on the side far from the support, and the support
A high-sensitivity emulsion layer may be provided on the side closer to. As a specific example, from the side farthest from the support, low sensitivity blue light
Color layer (BL) / High sensitivity blue sensitive layer (BH) / High sensitivity
Green photosensitive layer (G) I) /Low sensitivity green photosensitive layer (GL)/
High-sensitivity red-sensitive layer (R[I) /low-sensitivity red-sensitive layer (R
L) order, 2 or B) l/BL/GL/GH/R1 (
/RL or B) I/BL/Gll/CL/RL
/IIH, etc. It is also stated in Japanese Patent Publication No. 55-34932.
Sea urchin 1. From the side farthest from the support, blue-sensitive N/GH/
They can also be arranged in the order of RH/GL/RL. Also special
Specification No. 56-25738, No. 62-63936
blue from the side farthest from the support, as described in
Photosensitive layer/GL/RL/GH/RH arranged in the order
You can also do it. It is also stated in Japanese Patent Publication No. 49-15495.
The upper layer is the silver halide emulsion layer with the highest sensitivity, and the middle layer is the silver halide emulsion layer with the highest sensitivity.
A silver halide emulsion layer with a lower sensitivity than that, the lower layer
A silver halide emulsion layer with lower sensitivity than the middle layer is placed.
The photosensitivity gradually decreases toward the support.
Mention may be made of an arrangement consisting of three different layers. like this
Even if it is composed of three layers with different photosensitivity,
As described in specification No. 59-202464,
Medium sensitivity from the side away from the support in the same color-sensitive layer
The layers are arranged in the following order: emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer.
Good too. Other high anger breasts 1? I layer/Low sensitivity emulsion layer/Medium sensitivity emulsion
layer, or low-sensitivity emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer
They may be arranged in the order of the agent layer, etc. Also, if there are 4 or more layers, please change the arrangement as above.
stomach. As mentioned above, there are various types depending on the purpose of each photosensitive material.
The layered structure and arrangement of the ashes can be made. Contained in the photographic emulsion layer of the photographic photosensitive material used in the present invention
The preferred silver halide contains less than about 30 mole percent iodide.
Silver-containing silver iodobromide, silver iodochloride, or iodosalt odor
It is chemical silver. Particularly preferred is about 2 mol % to about 10 mol %.
Silver iodobromide or salt iodide containing up to 1% silver iodide
It is chemical silver. Silver halide grains in photographic emulsions are cubic, octahedral, and decahedral.
Those with regular crystals such as tetrahedrons, spherical, plate-shaped
crystals with irregular crystal shapes, such as crystals with twin planes,
It may be one with crystal defects or a composite form thereof.
. The grain size of silver halide is fine particles of approximately 0.2 microns or less.
However, the projected area diameter is about 10 microns.
It may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention include, for example,
Search Disclosure (RD) No. 17643 (December 1,978) pp. 122-23,
“1. Emulsion preparation
ion and types) m', and the same 187
16 (November 1979), page 64B, same issue 3071
05 (November 1989), pp. 863-865, and
Graphic “Physics and Chemistry of Photography”, Beaumontel
Published by P, GIaiides, Chemie et P
h1sique Photographyfque, P
aul Montel, 1967), Duffin,
"True Emulsion Chemistry", published by Focal Press (G, F, Du
ffin. Photographic Emulsjon Che
Mistry (Focal Press. 1966)), Zelikman et al.
”, published by Focal Press (V, L, Zelikm
anetal,, Making and Coati
ng Photographic Es+ul--5i
on, Focal Press, 1964), etc.
It can be prepared using the method described. U.S. Patent Nos. 3,574,628 and 3,655,39
No. 4 and British Patent No. 1,413,748, etc.
Also preferred are monodispersed emulsions. Also, tabular grains with an aspect ratio of about 3 or more
can also be used in the present invention. Tabular grains are
graphic science and engineering
Gutoff, Photographic Sci.
ence and Engineering), No.
14, pp. 248-257 (1970); U.S. Patent No. 4
, 434.226, 4,414.310, 4,
433.048, 4,439.520 and UK
It can be easily done by the method described in Patent No. 2.112.157 etc.
It can be simply prepared. Even if the crystal structure is -like, it is a halo whose inside and outside are different.
It may have a layered structure.
It is also possible to create epitaxial junctions with different compositions.
silver halide may be bonded, and for example silver halide may be bonded.
Bonding with compounds other than silver halide such as silver oxide and lead oxide
may also contain mixtures of particles of various crystalline forms.
May be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface.
However, even with the internal latent image type formed inside the particle, the surface and internal
Any type with a latent image may be used, but negative type
It is necessary that the emulsion is Of the internal latent image types,
Core/shell type interior described in Kaisho 63-264740
This core/shell type internal cavity, which may be an active emulsion,
The method for preparing image-type emulsions is described in JP-A-59-133542.
Are listed. The shell thickness of this emulsion varies depending on the development process, etc.
is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.
Yes. Silver halide emulsions are typically subjected to physical ripening, chemical ripening and
Use one that has undergone spectral sensitization. used in such processes.
The additives used are according to Research Disclosure 17
643, described in 18716 and 307105
The relevant sections are summarized in the table below. The light-sensitive material of the present invention includes grains of a light-sensitive silver halide emulsion.
size, particle size distribution, halogen composition, particle shape,
Milk of 211M or more that differs in at least one characteristic of sensitivity
Agents can be used mixed in the same layer. The particle surface described in U.S. Pat. No. 4,082,553
Blurred silver halide grains, U.S. Pat. No. 4,626,4
Inside the particle described in No. 98 and JP-A No. 59-214852
Silver halide particles coated with colloidal silver are coated with photosensitive silver.
a silver halide emulsion layer and/or a substantially non-light-sensitive parent layer;
It can be preferably used in an aqueous colloid layer. What is a silver halide grain whose inside or surface is coated?
, regardless of the unexposed or exposed areas of the photosensitive material.
silver halide grains that can be developed (non-imagewise)
Silver halide grains whose insides or surfaces are covered
The method for preparing the offspring is described in U.S. Pat. No. 4,626,498,
It is described in No. 59-214852. Core/shell type silver halide grains with fogged interior
The silver halide that forms the inner core of the child is the same halogen
Whether it has a different composition or a different halogen composition.
Silver halide coated inside or on the surface of good 0 grains
Silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide
A deviation can also be used. these covered ha
There is no particular limitation on the grain size of silver halide grains, but
The average particle size is 0.01 to 0.75 μm, especially
0゜05~0.6μ steel is preferable, and regarding the particle shape
There are no particular limitations on the particles, and regular particles may be used.
Polydisperse emulsions may be used, but monodisperse emulsions (silver halide grains
At least 95% of the amount or number of particles is ±4 of the average particle size
It is preferable that the particle size is within 0%.
. The present invention includes the use of non-photosensitive fine grain silver halide.
The non-photosensitive fine grain silver halide, which is preferably
During imagewise exposure to obtain an image, it is not exposed to light;
Silver halide that is not substantially developed during the development process.
It is fine particles and is preferably not fogged beforehand.
Delicious. Fine-grain silver halide has a silver bromide content of 0 to 100 moles.
silver chloride and/or silver iodide as required.
may contain silver iodide, preferably 0.5 to 10 moles of silver iodide.
%. Fine-grain silver halide has an average grain size (circle equivalent straight line of projected area)
The average value of diameter) is preferably 0.01 to 0.5 μ■, 0
．． 02 to 0.2μ songs are more preferable. Fine-grain silver halide is the same as ordinary photosensitive silver halide.
It can be manufactured using various methods. In this case, silver halide grains
The surface does not need to be optically sensitized or
Feelings are also unnecessary. However, when adding this to the coating solution,
In advance, triazole type, azaindene type,
Benzothiazolium or mercapto compounds or
or add a known stabilizer such as a zinc compound.
This layer containing fine silver halide grains is preferably coated with
Lloyd's silver can preferably be contained. The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/% or less.
Most preferably, it is 4.5 g/rrl or less. Known photographic additives that can be used in the present invention also include the above three additives.
It is stated in the research disclosure and below.
The relevant entries are shown in the table below. In addition, the deterioration of photographic performance due to formaldehyde F gas can be prevented.
In order to prevent this, U.S. Patent No. 4,411.987 and
Formaldehyde described in No. 4,435.503 and
Adding compounds that can be reacted and immobilized to photosensitive materials
is preferable. U.S. Patent M 4,740.454 applies to the photosensitive material of the present invention.
No. 4.788,132, JP-A-62-1853
No. 9, mercapto conversion described in JP-A No. 1-283551
It is preferable to contain a compound. The photosensitive material of the present invention is described in JP-A No. 1-106052.
, regardless of the amount of developed silver produced during the development process.
Blurring agents, development accelerators, silver halide solvents or the like
It is preferable to contain a compound that releases a precursor of
. National 11iR Public 11iy'1W08
No. 8104794, listed in Special Table of Contents No. 1-502912
Dye dispersed in a conventional manner or EP 31? , 308
No. A, U.S. Patent No. 4,420,555, JP-A-1-25
Preferably, the dye described in No. 9358 is included. Various color couplers are used in the photosensitive material of the present invention.
A specific example is the Research Disclosure mentioned above.
Jerite 17643, ■-C-G, and Nct
307105, ■-C-C
It is. As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401.752, No. 4,
No. 248,961, Special Publication No. 58-10739, British Special Publication No.
Allowance No. 1,425.020, No. 1.476.760
, US patent cylinder 3. s73, 19sa No. 4.314
．． No. 023, No. 4.511,649, European Patent No. 2
49.473A, etc. are preferred. As magenta couplers, 5-pyrazolone and pyrazo
A loazole type compound is preferable, and US Patent No. 4.31
No. 0,619, No. 4,351,897, European patent cylinder
No. 73,636, U.S. Patent No. 3.061.432,
No. 3゜725.067, Research Disclosure
- Stone 24220 (June 1984), JP-A-60-3
No. 3552, Research Disclosure 81124
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 60-35730, No. 61-72238, No. 60-35730, No.
No. 55-118034, No. 60-185951, United States
Patent tube 4゜500,630, same number 4,540,654
No. 4,556.630, International Publication Ho8810
Particularly preferred are those described in No. 4795 and the like. As cyan couplers, phenolic and naphthol
The system coupler is removed, and U.S. Patent No. 4,052, 212
No. 4.146.396, No. 4,228.23
No. 3, No. 4.296.200, No. 2,369.9
No. 29, No. 2,801.171, No. 2.772.
No. 162, No. 2.895.826, No. 3.772
．． No. 002, No. 3.758, 308, No. 4.33
No. 4.011, No. 4,327,173, West German Patent Publication
Opening No. 3゜329.729, European Patent No. 121.365
A, No. 249°453A, U.S. Patent No. 3.446
, No. 622, No. 4,333,999, No. 4.77
No. 5.616, No. 4,451.559, No. 4,4
No. 27,767, No. 4,690,889, No. 4.
2.54゜212, 4.296.199, JP
Those described in No. 61-42658 and the like are preferred. A typical example of a polymerized dye-forming coupler is
Allowance No. 3.451.820, No. 4,080,211
, No. 4,367.282, No. 4,409.320
No. 4.576°910, British Patent No. 2.102.
No. 137, European Patent No. 341゜188A, etc.
ing. As a coupler whose coloring dye has an appropriate diffusivity, American
National Patent No. 4,366.237, British Patent No. 2.125
．． 570, European Patent No. 96,570, West German Patent (Public Patent)
3,234,533 is preferred. Colored coupler to correct unnecessary absorption of color pigments
– Research Disclosure Seed 17643■
-G section, ■-G section of the same product 307105, U.S. Patent No. 4,
No. 163.670, Special Publication No. 57-39413, United States Special Publication No.
Permit No. 4,004,929, No. 4,138,258
, the one described in British Patent No. 1,146,368 is preferred.
Also, as described in U.S. Pat. No. 4,774,181
The fluorescent dye released during coupling produces a colored dye.
Couplers that correct unwanted absorption and U.S. Patent No. 4,777
．． It may react with the developing agent described in No. 120 to form a dye.
A coupler having a dye precursor group as a leaving group
It is also preferable to use Coupling releases photographically useful residues
Compounds can also be preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F term and the same 307105, ■-F
The patent described in JP-A No. 57-151944,
No. 57-154234, No. 60-184248, No. 6
No. 3-37346, No. 63-37350, U.S. Patent 4
, No. 248,962, No. 4,782.012.
Preferably. Releases nucleating agent or development accelerator in image form during development
As a coupler, British Patent No. 2,097,140,
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.
Also, JP-A No. 60-107029, No. 60-2 “52
340, JP-A No. 1-44940, JP-A No. 1-45687
Through the redox reaction with the oxidized form of the developing agent described in the issue,
Releases fogging, development accelerators, silver halide solvents, etc.
Also preferred are compounds such as Other compounds that can be used in the photosensitive material of the present invention
As described in U.S. Patent No. 4.130.427 etc.
Competitive coupler, U.S. Pat. No. 4,283.472;
No. 4,338.393, No. 4,310,618, etc.
The multi-equivalent coupler described in JP-A-60-185950,
DIR redox described in JP-A-62-24252 etc.
Compound releasing coupler, DIR coupler releasing coupler, D
IR coupler releasing redox compound or DIR Redo
Ox-releasing redox compound, European Patent No. 173゜30
No. 2A, recoloring after separation described in No. 313,3088.
A coupler that releases a dye, R, D, Nα11449,
24241, JP-A No. 61-201247, etc.
Bleach-promoting side-emitting coupler, U.S. Pat. No. 4,555,47
Gantt release coupler described in No. 7, etc., JP-A-63-7
Coupler releasing leuco dye described in No. 5747, US
Releases the fluorescent dye described in National Patent No. 4゜774,181
Examples include couplers that do. The couplers used in the present invention can be obtained by various known dispersion methods.
can be introduced into light-sensitive materials. An example of a high boiling point solvent used in the oil-in-water dispersion method is a U.S. patent.
No. 2.322.027, etc. The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalate ester
esters (dibutyl phthalate, dicyclohexyl phthalate)
di-2-ethylhexyl phthalate, decylphthalate
rate, bis(2,4-sheet amyl phenyl) phthalate
bis(2,4-di-t-amylphenyl)isoph
tallate, bis(1,1-diethylpropyl)phthalate
esters of phosphoric or phosphonic acids (such as
Phenyl phosphate, tricresyl phosphate, 2
-ethylhexyl diphenyl phosphate, tricyclo
hexyl phosphate, tri-2-ethylhexyl phosphate
phate, tridodecyl phosphate, tributoxye
chill phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate
, dodecyl benzoate, 2-ethylhexyl-p-h
droxybenzoate, etc.), amino, do (N, N-di)
Ethyldodecaneamide, N,N-diethyllaurylamide
(de, N-tetradecylpyrrolidone, etc.), alcohols
or phenols (isostearyl alcohol, 2.
4-tert-amylphenol, etc.), aliphatic
Carboxylic acid ester R (bis(2-ethylhexyl)cetate)
Vacate, dioctyl azelate, glycerol trib
Thilate, isostearyl lactate, trioctyl lactate
trate, etc.), aniline derivatives (N, N~dibutyl-
2-butoxy-5-tert-octylaniline, etc.)
, hydrocarbon R (paraffin, dodecylbenzene, diiso
(propylnaphthalene, etc.). In addition, as an auxiliary solvent, it is preferable that the springing point is about 30°C or higher.
cannot use organic solvents at temperatures above 50°C and below approximately 160°C.
Typical examples include ethyl acetate, butyl acetate, and propioacetate.
ethyl phosphate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide
Examples include. Latex dispersion process, effects and latex for impregnation
Specific examples include U.S. Patent No. 4,199,363,
Patent publication [(OLS) No. 2.541.274 and
No. 2°541.230, etc. The color photosensitive material of the present invention contains phenethyl alcohol.
JP 63-257747, JP 62-272248
and the 1,2-base described in JP-A No. 1-80941.
nisothiazolin-3-one, n-butyl p-hydro
Roxybenzoate, phenol, 4-chloro-3,5
-dimethylphenol, 2-phenoxyethanol,
2-(4-thiazolyl)benzimidazole, etc.
It is preferable to add a seed preservative or a fungicide. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Nα17643, page 28, same amount 18716, 647
From the right column on page 648, and the same number Nα307105.
It is described on page 879.゛The photosensitive material of the present invention has a total hydrophilic color on the side having the emulsion layer.
It is preferable that the total thickness of the id layer is 28 μm or less.
23μ or less is more preferable, and 18μ or less is even more preferable.
Preferably, 16 μm or less is particularly preferable, and the membrane swelling rate is
degree TI/! is preferably 30 seconds or less, more preferably 20 seconds or less.
The preferred JII thickness is at 25°C and 55% relative humidity.
(means the film thickness measured in 2 days, film swelling rate T, /2
is measured according to methods known in the art.
For example, Knee Green (1, Green
Photographic Science and
・Engineering (Pbotogr, SciJng,
), 19%, No. 2, 124 = of the type described on page 129
Measured by using a swellometer (swelling membrane)
71/□ was processed with color developer at 30℃ for 3 minutes and 15 seconds.
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when
, is defined as the time required to reach the saturated film thickness of 172. The membrane swelling rate T l/x is determined by gelatin as a binder.
ni f! Adding a film agent or adjusting the aging conditions after application
It can be adjusted by changing. Also, swelling
The swelling rate is preferably I50 to 400%.
From the maximum swollen film thickness under the stated conditions, the formula = (maximum swell
It can be calculated according to the formula: film thickness - film thickness)/film thickness. The photosensitive material of the present invention has a dry layer on the side opposite to the side having the emulsion layer.
A hydrophilic colloid layer with a total dry thickness of 2 μm to 20 μm (
This bank is preferably provided with a back layer (referred to as a back layer).
The layers include the aforementioned light absorbers, filter dyes, and UV absorbers.
agent, anti-static agent, hardening agent, binder, plasticizer,
It is preferable to include lubricants, coating aids, surfactants, etc.
Preferably, the swelling rate of this bank layer is 150 to 500%.
Delicious. The photosensitive material of the present invention is a color reversal film, a color
– Duplicating film, color reversal
Color lever for vapor and overhead projectors
- monkey film, color negative film, color film for movies
Gafilm, color paper, color positive film, etc.
It is used for. Next, the processing solution and processing steps for the color reversal photosensitive material of the present invention
I will explain about it. Among the processing steps of the color reversal photosensitive material of the present invention, black development
The steps from to color development are as follows. ■) Black and white development - water washing, reversal, and color development 2) Black and white development
-Water wash, one light reversal, one color development 3) Black and white development -Water wash, one color development
The water washing steps of development steps 1) to 3) are all performed as described in U.S. Patent Nos. 4 and 8.
Instead of the rinsing process described in No. 04,616,
It is possible to improve the efficiency and reduce waste liquid. Next, the steps after color development will be explained. 4) Color development - Adjustment - Bleaching - Fixed - Washing - Stable 5) Color development
Development - Washing with water, bleaching, constant coloring, washing with water - stable 6) Color development - tone
Separation - Bleaching - Constant washing - Stable - Washing - Stable 7) Color development - Washing - Bleach - Washing - Stable - Washing - Stable 8) Color development - Bleaching - Constant washing - Stable 9) Color development -
Bleach 2 Bleach fixing - Water washing 10) Color development - Bleach 1 Bleach
White fixing, constant setting, washing with water, stable 11) Color development - bleaching, washing with water, fixed setting, washing with water, stable 12)
Color development - Adjustment - Bleach fixing - Washing - Stability 13) Color development
- Washing - Bleach fixing - Washing - Stable 14) Color development - Bleach fixing
15) Color development, constant color development, bleaching, fixing, and washing
In the stabilizing process 4) to 15), the stabilizing process
The immediately preceding water washing step may be removed, or conversely, the final washing step may be removed.
The stabilization step does not have to be carried out, the above steps l) to 3
) and any one of the steps 4) to 15).
The dots are connected to form a color reversal step. Next, the processing liquid for the color reversal processing step of the present invention will be explained.
do. The black and white developer used in the present invention contains a known developing agent.
Can be used. As a developing agent, dihydroxy
Benzenes (e.g. hydroquinone), 3-pyrazoli
Don! ! (e.g. 1-phenyl-3-pyrazolidone)
, amine phenols (e.g. N-methyl-p-aminophenols)
(phenol), 1-phenyl-3-pyrazolines, a
Scorbic acid and as described in U.S. Pat. No. 4,067.872.
1,2,3,4-tetrahydroquinoline ring and into
Heterocyclic compounds such as those fused with a ren ring can also be used alone.
Alternatively, they can be used in combination. The black and white developer used in the present invention may contain preservatives (e.g.
e.g. sulfites, bisulfites), buffers (e.g. carbonate),
salt, boric acid, borate, alkanolamine), alkaline agent
(e.g. hydroxides, carbonates), dissolving tablets (e.g.
(lyeethylene glycols and their esters), pH
1 lil stimulants (e.g. organic acids such as acetic acid), aggravating agents (
For example, quaternary ammonium salts), development accelerators, surfactants
containing agents, antifoaming agents, hardening agents, viscosity imparting agents, etc.
I can do it. As a silver halide solvent in the black and white developer used in the present invention,
It is necessary to include an active compound, but usually the above
The sulfite added as a preservative plays this role.
as sulphites and other usable silver halide solvents.
Specifically, KSCN. Na 5CNSKzSO,, NazSOz, Kr5x
C1s, Na25z05, K2SiO3, Nazsz
○, etc. In addition, a development accelerator is used to impart a development accelerating effect.
However, in particular, the compound described in JP-A No. 57-63580
or organic thioether compounds can be used. These halogenated! ! Use too little solvent
Too much will slow down the development process, while too much will cause halogenation.
To create a fog on the side of the silver hole, use the amount you prefer.
However, the amount can be easily determined by one skilled in the art.
It's Chino. For example, 5CN- is developer II! 0.005~0.
02 mol, especially 0.02 mol. O1 to 0.015 mol
Preferably, so,"- is 0.05 to 1 mol, especially 0.05 to 1 mol.
The amount is preferably 1 to 0.5 mol. The black-and-white developer of the present invention includes various types of beef resin for the purpose of water softening.
Compounds are used. These chelate compounds include
, aminopolycarboxylic acid explained in the color developer section
, organic phosphonic acids, and phosphonocarboxylic acids.
It is preferable that The black and white developer of the present invention also contains the above-mentioned sulfite as a preservative.
In addition to salt, use the various compounds explained in the color developer section.
Can be added. In the black and white development process of the present invention, for the purpose of preventing development fog,
Various antifoggants may be added. Antifoggants include potassium bromide, sodium bromide,
Alkali metal halides such as potassium iodide and organic
The organic antifoggant, which is preferably an antifoggant, includes:
For example, benzotriazole, 6-nidropenzimitaso
ol, 5-nitroindazole, 5-methylbenzo
Triazole, 5-nitrobenzotriazole, 5-k
Lolo-benzotriazole, 2-thiazolyl-benzi
Midazole, 2-thiazolylmethyl-benzimidazole
Nitrogen-containing heterocycles such as hydroxyl, hydroxyazaindolizine
Compound and 1-phenyl-5-mercaptotetrazole
2-mercaptobenzimidazole, 2-mercaptobe
mercapto W-substituted heterocyclic compounds such as nzothiazole;
Furthermore, aromatization of mercapto substitutions such as thiosalicylic acid
Compounds can be used. These antifoggants are
, eluted from the color reversal photosensitive material during processing, and these
Including those that accumulate in the developer. The pH value of the developer solution adjusted in this way is the desired concentration.
is selected to a sufficient extent to give contrast with, but approximately
It ranges from 8.5 to about 11.5. In order to perform sensitization using such a black and white developer, standard
This process can be done by extending the time up to three times as long as semi-processing.
If you increase the treatment temperature, it will extend the time for exacerbation treatment.
Can be shortened. A known fogging agent is used in the reversal bath used after black and white development.
can be included. That is, stannous ion-organophosphorus
Acid complex salts (U.S. Pat. No. 3,617°282), No.
1 Tin ion organic phosphonocarboxylic complex salt (Special Publication No. 5
6-32616), stannous ion-aminopoly
Carboxylic acid complex salt (U.S. Pat. No. 1,209,050)
stannous ion complex salts such as books), borohydride compounds (
U.S. Patent No. 2,984,567), complex
Cyclic amine borane compound 171 (British Patent No. 1.011,0
00 specification), etc.
The pH of the turn bath (reversal bath) ranges from acidic to alkaline.
pH ranges from 2 to 12, preferably
is in the range of 2.5 to 10, particularly preferably 3 to 9.
Even if light reversal processing is performed by re-exposure instead of a reversal bath,
It is also common to add the fogging agent mentioned above to the color developer.
Therefore, the reversing step can also be omitted. The color developer of the present invention is preferably an aromatic primary amine.
0, which is an alkaline aqueous solution whose main component is a color developing agent.
Aromatic primary amine color developer used in color developer
Aminophenol compounds are also used as medicines, but p
-Phenylenediamine derivatives are preferred, typical examples are shown below.
are shown, but are not limited to these. D-IN, N-diethylnyl-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-lauryl
mino)toluene D-44-(N-ethyl-N-(β-hydroxyethyl
) Aminocoaniline D-52-methyl-4-[N-ethyl-N-[β-hydro
(oxyethyl) aminocoaniline D-64-amino-3-methyl-N-ethyl-N-[β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenyl
ethyl) methanesulfonamide D-8N, N-dimethyl
-P-phenylenediamine D-94-amino-3-methyl-N-ethyl-N-meth
xyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-ethoxyethylaniline D-114-amino-3-methyl-N=ethyl-N-β
-Butoxyethylaniline Particularly preferred among the above P-phenyl diamine derivatives
are exemplary compounds D-2, D-4, D-5 and D-6
. In addition, these p-phenylenediamine derivatives are sulfate
, hydrochloride, sulfite, P-1-luenesulfonate, etc.
The use of the aromatic-grade amine developing agent, which may be a salt of
The dosage is preferably about 0.1 g to about 20 g per 11 developer solution.
, more preferably at a concentration of about 0.5 g to about 15 g. In the present invention, the color developer contains substantially benzyl alcohol.
Preferably, it contains no benzyl alcohol.
Color developing solution that does not contain alcohol is benzyl alcohol.
The concentration of the developer solution is 11 equivalents') 3X10-" molar or less,
Color developer preferably free of benzyl alcohol
shows. The color developing solution of the present invention preferably contains a sulfite.
Sulfites are sodium sulfite and potassium sulfite.
um, sodium bisulfite, bisulfite power, lium, meth
Lists sodium bigrite, potassium metabigite, etc.
be able to. The preferred amount of sulfite added is sodium sulfite.
In terms of thorium, 1Xl0 per color developer If
mol to 5XIO-”mol, more preferably lXl
0-'mol-5X10-''mol, more preferably
The color developing solution of the present invention ← directly preserves the color developing agent.
Various hydroxylamines as compounds, patent application 1986
- Hydroxamic acids described in No. 186559, No. 61-1
The phenol described in No. 88742 and No. 61-203253
α-hydroxy as described in No. 61-188741
Ketones, α-aminoketones and/or 61-18
It is preferable to add various IiRs described in No. 0616. In addition, in combination with the above compounds, patent application No. 61714782
No. 3, No. 61-166674, No. 61-165621
No. 61-164515, No. 61-170789
, and monoamines described in No. 61-168159, etc.
, No. 61-173595, No. 61-164515,
Diamines described in No. 61-186560, etc., No. 61
-165621 and 61-169789
Polyamines, polyamine described in No. 61-188619
nitroxy radicals described in No. 61-197760
61-186561 and 61-19741
Alcohols described in No. 9, No. 61-198987
and the tertiary oximes described in No. 61-265149.
Preference is given to using amines. Other preservatives include JP-A No. 57-44148 and the same.
57-53749, JP-A-59-1999-
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
Aromatic polyhydroxy compounds described in No. 746,544, etc.
may contain as necessary, especially aromatic polyhydro
Preference is given to the addition of oxygen compounds. The color developing solution used in the present invention preferably has a pH of 9 to
14, more preferably 9 to 13, and in the color developer
contains other known color developer component compounds.
can be done. In order to maintain the above pH, it is recommended to use various buffers.
preferable. Specific examples of buffering agents include sodium carbonate and potassium carbonate.
Mu, Sodium Bicarbonate, Potassium Bicarbonate, Trisodium Phosphate
Lium, tripotassium phosphate, disodium phosphate, phosphorus
acid dipotassium, sodium borate, potassium borate, tetra
Sodium borate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate)
), 〇-H)=potassium loxybenzoate, 5-sulfo-
Sodium 2-hydroxybenzoate (5-sulfosalic acid)
5-sulfo-2-hydroxybenzoic acid), 5-sulfo-2-hydroxybenzoic acid
potassium acid (potassium 5-sulfosalicylate), etc.
can be given. However, the present invention
It is not limited to compounds. The amount of the buffer added to the color developing solution is 0.1 mol/!
It is preferably at least 0.1 mol/! ~0.
Particularly preferred is 4 mol/2. In addition, the color developer contains calcium and magnesium.
as an anti-settling agent or to improve the stability of color developers.
For this purpose, various bovine rate agents can be used. Yes as a chelating agent! R acid compounds are preferred, e.g.
Aminopolycarboxylic acids, organic phosphonic acids, phosphono
Examples include carboxylic acids. Specific examples are shown below, but are not limited to these.
. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylene
Ndiaminetetraacetic acid, N,N,N-trimethylenephosphone
acid, ethylenediamine-N,N. N',N''-tetramethylenephosphonic acid, transsic
lohexanediaminetetraacetic acid, 1,2-di7minobloban
Tetraacetic acid, hydroxyethyliminodiacetic acid, glycol
terdiaminetetraacetic acid, ethylenediamine orthohydro
xyphenylacetic acid, 2-phosphonobutane-1,2,4-
) Ricarboxylic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, N,N'-bis(2-hydroxybenzi
) Ethylenediamine-N,N'-diacetic acid,
Two or more rate agents may be used in combination, if necessary. The amount of these chelating agents added is determined by the amount of metal ions in the cough color developer.
It is sufficient as long as the amount is sufficient to block the on.0 For example, 12
It is about 1 g to 10 g per serving. An optional development accelerator may be added to the color developing solution if necessary.
However, Japanese Patent Application Laid-Open No. 52-49829 and
P-phenylenediamine represented by No. 50-15554
Compounds, JP-A-137726, 1972, JP-A No. 137726, 1973
-30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium represented by No. 2-43'429, etc.
Salts, U.S. Pat. No. 2,494,903, U.S. Pat. No. 3,128
゜No. 182, No. 4,230,796, No. 3.253.
No. 919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,
No. 482,546, No. 2,596,926 and No. 3.
Amine compounds described in No. 582,346 etc.,
No. 7-16088, No. 42-25201, U.S. Patent No.
No. 3,128,183, Special Publication No. 41-11431, same
No. 42-23883 and U.S. Patent No. 3,532,501
Polyalkylene oxide represented by No. 1, etc., and others 1
-Phenyl-3-pyrazolidones, imidazoles, etc.
can be added as necessary. In the present invention, any antifoggant may be used as necessary.
can be added. As an antifoggant, sodium chloride
, potassium bromide, potassium iodide etc.
Genides and antifoggants can be used. organic turnip
For example, benzotriazole, 6-nitriazole,
Dropenzimidazole, 5-nitroisoindazole
, 5-methylbenzotriazole, 5-nitrobenzoto
Riazole, 5-chloro-benzotriazole, 2-thi
Azolyl-benzimidazole, 2-thiazolylmethyl
-benzimidazole, indazole, hydroxyaza
Nitrogen-containing heterocyclic compounds such as indolizine and adenine
This can be cited as a representative example. The color developing solution used in the present invention contains a fluorescent whitening agent.
The fluorescent whitening agent may include 4゜4゛-diamide.
No-2,2'-disulfostilbene compounds are preferred
, the amount added is O~5g/I! , preferably 0.1g to 4
g/j! It is. In addition, alkyl sulfonic acid, arybosulfonate may be added as necessary.
Various interfaces of acids, aliphatic carboxylic acids, aromatic carboxylic acids, etc.
An activator may also be added. The processing temperature with the color developing solution of the present invention is preferably 20 to 50°C.
Preferably, it is 30 to 40°C. Processing time is 20 seconds to 8 minutes
, preferably 30 seconds to 6 minutes. The smaller the amount of replenishment, the better
Preferably, the distance is 100 to 3000 m per photosensitive material, preferably
Preferably 100 to 2500 paper, more preferably 1
00-2000d. In addition, the color developing bath may be exposed to two or more baths as necessary.
Replenish the color developer replenisher from the pre-bath or last bath and proceed with development.
The imaging time may be shortened or the amount of replenishment may be reduced. In addition, the color developing solution of the present invention contains, for the purpose of adjusting FtFi,
Oxidized products of color developing agents such as citradinic acid, J acid, H acid, etc.
A colorless compound is produced by reacting with the so-called
Competing compounds can be included. The silver halide color photographic light-sensitive material of the present invention can be developed by color development.
Post-bleaching or bleach-fixing. These processes
It is done immediately without going through the color developing agent processing step.
May be used to prevent unnecessary post-development, air capping, and desilvering.
In order to reduce the amount of color developer brought into the process,
Ingredients such as sensitizing dyes and dyes contained in photographic materials
Washing out the color developing agent impregnated in the photosensitive material
In order to make it harmless, stop and adjust it after the color development process.
Bleaching treatment or bleach-fixing after processing steps such as conditioning and washing with water.
May be processed. The above adjustment solution contains ethylenediaminetetraacetic acid, diethyl
triaminepentaacetic acid, 1,3-propanediaminetetraacetic acid
, aminopolycarbonate such as cyclohexanediaminetetraacetic acid
Rubonic acids, sodium sulfite, ammonium sulfite
sulfites, such as thioglycerin, aminoethanethi
It is explained in the bleaching solution such as ol, sulfoethanethiol, etc.
Various bleach accelerators as described below can be included. Also
For the purpose of preventing scum, U.S. Patent No. 4,839,262
Sorvita of fatty acids substituted with ethylene oxide as described
esters, U.S. Pat. No. 4,059°446 and Lisa
Arch Disclosure Volume 191, 19104 (1
Containing polyoxyethylene compounds etc. described in 980)
It is preferable to have it. As a bleaching agent used in bleach and/or bleach-fix solutions
are ferric complex salts of aminopolycarboxylic acids, peroxides (e.g.
(sodium persulfate) can be used, but aminopolymer
Ferric carboxylic acid complex salts are preferred.
As for recarboxylic acid, the following compounds can be used.
preferable. Ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid
Acetic acid, glycol ether diamine tetraacetic acid, cyclohexyl
Sandiaminetetraacetic acid, 1,4-diaminobutanetetraacetic acid,
1.2-Propylenediaminetetraacetic acid, thioglycole
-terdiaminetetraacetic acid, 1,3-butylenediaminetetraacetic acid
acids, methyliminodiacetic acid, etc. The amount of bleach mentioned above is based on the bleach solution or bleach-fix solution.
0.05 mol to 1 mol, preferably 0.1 mol to 1 mol per 12
It is 0.5 mole. In addition, the above aminopolycarboxylic acid
Using two or more compounds of diiron complex salts together with bleach
It can also be used as In this case, the mixing ratio of both is 1
:10 to 10:1 is preferable, and both iron t"salt concentration
The total amount is 0.05 mol to 1 mol, preferably
Preferably it is 0.1 to 0.5 mol. Other bleaching solutions and/or bleach-fixing solutions of the present invention include those mentioned above.
In addition to the aminopolycarboxylic acid iron (I[[) complex, aminopolycarboxylic acid iron (I[[)]
Recarboxylate salts can be added. The preferable addition amount is 0.0001 mol to 0.1 mol/! Yo
More preferably, it is 0.003 to 0.05 mol/2. Aminopolycarboxylic acids and their ferric complex salts are usually
Preferably used in the form of potash metal or ammonium salts.
In particular, ammonium salt has excellent solubility and bleaching properties.
It is preferable. Also, bleaching solutions and/or bleaching containing the above-mentioned ferric ion salts.
The fixer contains metal ion complex salts other than iron such as cobalt and copper.
It may be included. The bleaching solution and/or bleach-fixing solution of the present invention includes various bleaching solutions.
Accelerators can be added. Such bleach accelerators are described, for example, in U.S. Pat.
No. 3,893,858, German Patent No. 1,290
, No. 812, British Patent No. 1゜138.842
Specification, Japanese Patent Application Laid-Open No. 53-95630, Research Day
In Scrooger No. 17129 (July 1978 issue)
Compounds having a mercapto group or disulfide group as described
Preferably. The amount of bleach accelerator added is 0.0 per 11 liquids with bleaching ability.
The amount is 1 g to 20 g, preferably 0.1 g to 10 g. The bleaching solution and/or bleach-fixing solution constituting the present invention includes
In addition to whitening agents and the above compounds, bromides, such as potassium bromide
sodium bromide, ammonium bromide or chloride, e.g.
For example, potassium chloride, sodium chloride, ammonium chloride
can include rehalogenating agents such as. re-halogen
The concentration of the bleaching agent is 11 to 5 mol per 11 mol of bleaching solution, preferably
The preferred amount is 0.5 to 3 moles. In addition, sodium nitrate,
Nitrates such as ammonium nitrate, boric acid, borax, sodium metaborate
Thorium, acetic acid, sodium acetate, sodium carbonate, charcoal
potassium acid, phosphorous acid, phosphoric acid, sodium phosphate, citric acid
, sodium citrate, tartaric acid, etc.
One or more types of inorganic acids, organic acids, and their salts, etc.
Adding known additives that can be used in bleaching solutions
I can do it. The bleach-fix solution and/or fix solution of the present invention includes a fixing agent.
Thiog acid salts can be used. Addition of thiosulfate
The amount is 0.1 mol/l-3 mol/l and 0.3 mol/l
/! ~2 mol/j! is preferred. Examples of thiosulfate compounds include ammonium thiogate and thiosulfate.
sodium acid, potassium thiosulfate, calcium thiosulfate
, magnesium thiosulfate, etc., but the solubility is
Thiosulfur
Ammonium acid is preferred. The fixing agent or fixing agent of the bleach-fixing solution and/or fixing solution of the present invention
In addition to the above-mentioned thiog acid compounds, thiocyanine is used as an adhesion promoter.
acid compounds (especially ammonium salts), thiourea, thioether
ether, urea, etc. can be used. These auxiliary
The concentration of the fixing agent or fixing accelerator is thiosulfate.
It is 1.11 to 3.0 mol/j2 together with the compound,
Preferably 1.4 to 2.8 mol/i! It is. The bleach-fix solution and/or fix solution of the present invention may contain a preservative.
Sulfites such as sodium sulfite, potassium sulfite
ammonium sulfite and hydroxylamine, hydrogen
It can contain dorazine and the like. Furthermore, various
Optical brighteners, antifoaming agents, surfactants, polyvinyl pines, etc.
Containing fm solvents such as lolidone and methanol
However, especially as a preservative, the patent application No. 60-2838
Using the sulfinic acid compound described in Specification No. 31
is preferred. Furthermore, for the purpose of stabilizing the liquid, various aminopolycarbon #1
It is preferable to add 1s or organic phosphonic acids. In particular, 1-hydroxyethylidene-1,1-diphosphone
Acid is effective. The amount of these additions is 0.01 to 0.
．． 3 moles/! , preferably 0.05 to 0.2 mol/! in
It is particularly effective in fixing solutions. The pH of the bleaching solution and/or bleach-fixing solution of the present invention is 9 to 1.
Generally, but preferably 7.5 to 1.5, most preferably
Preferably, it is 7.0 to 2.0. For bleaching solutions, 5.0 to 2.0 is particularly preferred. In a preferred pH range, there is less bleaching blade smearing and
Excellent silver performance. The pH of the fixer of the present invention is generally 9.0 to 5.0.
However, 7.5 to 5.5 is particularly preferable. The replenishment amount of the bleaching solution and/or bleach-fixing solution of the present invention is
50IIIl per fee! ~3000 ml, preferably
is 100I11 to l000d. The amount of fixer replenishment is 300d per photosensitive material.
3000d is preferable, but 300d or more is more preferable.
There are 1,000 papers. However, the above replenishment amount is
, if you perform oxidation regeneration of the processing solution, silver recovery treatment, etc.
can be reduced to a small amount. In addition, as a replenishment method for the above desilvering process, each treatment
Refill the bath with the corresponding replenisher solution and discard the overflow solution.
Although it is normal to use the overflow liquid from the pre-bath as
Direct flow replenishment method leading to the subsequent bath or overflow of the subsequent bath.
-Can also be used with a countercurrent replenishment system that leads the liquid to the pre-bath.
For example, the wash water or the overflow of the stabilizing bath can be transferred to the fixing bath.
Alternatively, it can also be led to a bleach-fixing bath. The shorter the total time of the desilvering process of the present invention, the more effective the present invention is.
is obtained significantly. The preferred time is 1 minute to 1 minute, and
It is preferably 1 minute to 6 minutes. Also, the processing temperature is 25℃
~50°C, preferably 35°C to 45°C. Like
In the new temperature range, the desilvering rate improves and the processing speed increases.
The occurrence of stains after treatment is effectively prevented. In the desilvering process of the present invention, stirring is strengthened as much as possible.
In order to more effectively exhibit the effects of the present invention,
It is preferable. A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, U.S. Patent No. 4,758
．． A processing liquid is applied to the emulsion surface of the photosensitive material described in the specification of No. 858.
Method of colliding jets and Japanese Patent Application Laid-Open No. 183461/1986
A method of increasing the stirring effect using a rotating means, and furthermore,
Be careful not to let the wiper blade attached to the emulsion surface come into contact with the emulsion surface.
Stirring is achieved by moving the optical material and creating turbulence on the emulsion surface.
How to improve the stirring effect, increase the circulation of the entire processing liquid @ volume
Here are some ways to do it. Such means for improving agitation are
Effective in white liquor, bleach-fix solution, and fixer solution.
Ru. Improved agitation improves the supply of bleach and fixing agent into the membrane on the pore side.
It is thought that this increases the desilvering speed as a result. In addition, the above-mentioned agitation improvement means can be used when a bleach accelerator is used.
more effective and significantly increases the promoting results or bleaching
It is possible to eliminate the fixation inhibiting effect caused by the promoter. The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
No. 59, Re5earch DisclosureIt
em k29118 (July 1988), US Patent
Photosensitive material conveyor described in specification No. 4,758,858
The above-mentioned JP-A-60-19 preferably has steps.
As described in No. 1257, such conveyance means
It is possible to significantly reduce the amount of processing liquid brought into the post-bath.
It is highly effective in preventing the performance deterioration of
It is also preferable to obtain such an effect by the treatment in each step.
Particularly effective in shortening processing time and reducing the amount of processing solution replenishment
. These stirring enhancement methods are effective for processes other than the desilvering process.
, applied to the water washing process and developing process to shorten processing time and replenish
It is desirable to reduce the amount. The processing method of the present invention includes the above-mentioned color development, bleaching, and bleach fixing.
It consists of processing steps such as adhesion and fixing. After the bleach-fixing or fixing process, water washing and stabilization are required.
It is common practice to carry out processing steps such as oxidation.
However, after bathing with fixing ability, it is safe to use without substantial washing with water.
A simple processing method that performs standardization processing can also be used.
. The rinsing water used in the rinsing process may contain known
1 that can contain additives, for example, inorganic phosphoric acid
, aminopolycarboxylic acid, fffl phosphoric acid, etc. for hard water softening.
Disinfectant, fungicide that prevents the growth of various bacteria and algae.
disinfectants (e.g., isothiazolones, organochlorine disinfectants,
(e.g.), to prevent drying load and unevenness.
Surfactants such as these can be used. Or L,
E. West. "WaL'er Quality Cr1teria"
, Phot, Sci, and Eng. Vol.9. Na6. Pages 343-359 (19
65) etc. can also be used. The stabilizer used in the stabilization process stabilizes the dye image.
For example, a buffer with a pH of 3 to 6 is used.
aldehydes (e.g. geltal aldehydes)
A liquid containing hydride) can be used. Holma
Phosphorus is undesirable from a pollution standpoint, so it may be added to the stabilizing solution as necessary.
Ammonium compound, Bi, Aj! metal compounds such as
Fluorescence enhancers, chelating agents (e.g. EDTA
1-hydroxyethylidene-1,1-diphosphonic acid),
Use of fungicides, fungicides, dura mater, surfactants, etc.
As an anti-fungal agent, 5-chloro-2-methylene
l-isothiazolin-3-one, 1゜2-benziiso
Thiazolone compounds such as thiazolin-2-one f<blind motion
It is. In addition, the stabilizer contains thiosulfur introduced by the photosensitive material.
Addition of alkanolamine to prevent sulfidation of acid ions
The preferred use of alkanolamines is
No. 4,786,583. Also, - For boat fishing, the stabilizing liquid contains formalin.
In the present invention, it may not be used. The pH of the stabilizer of the present invention is 3 to 8, but preferably
, 5-7. The temperature of the stabilizing solution is preferably 5°C to 45°C.
temperature, more preferably 10°C to 40°C. In addition, a multistage countercurrent method is preferable for the water washing process and stabilization process.
, the number of stages is preferably 2 to 4, two or more types of stable
The liquid can be applied in multiple stages, and the amount of replenishment is per unit area.
1 to 50 times the amount brought in from the prebath, preferably 2 to 30 times
, more preferably 2 to 15 times. The effect of the buried wood invention is that the processing time of water washing and stabilization process is short.
Total processing time of water washing and stabilization process from the point of view of rapid processing.
is preferably 10 to 50 seconds, especially 10 to 30 seconds.
The effect is significant. In addition, the effect of the buried wood invention is that the amount of replenishment during washing and stabilization processes is small.
50ai per ITf of photosensitive material! ~400m is preferable
Especially, 50 to 200 d is particularly preferable. The water used in these washing steps or stabilization steps
In addition to tap water, Ca
, Mgfi degree 5 tag/j! Deionization treatment
Sterilized by water, halogen, ultraviolet germicidal lamp, etc.
Preferably, water is used. In addition, the overflow liquid from the water washing process or stabilization process is used as a pre-bath.
Use a method of flowing the liquid into a bath having a fixing ability of
This also makes it possible to reduce the amount of waste liquid. ('Example P) The present invention will be explained in more detail with reference to Examples below.
However, the present invention is not limited thereto.
. Example 1 Preparation of sample 101 Triacetic acid film with a thickness of 205 μm with primer coating on both sides of the film
Each of the following compositions was deposited on a cellulose film support.
A multilayer color photosensitive material consisting of layers was prepared, and sample 101 and
did. The coating amount of each composition is the value per 1rrf of sample. For silver halide and colloidal silver, the equivalent amount of silver is
The converted weight is shown. 1st layer: Antihalation layer black colloidal silver 0.25g gelatin
1.9g UV absorber U-1
0,04g Ultraviolet absorber U-20,1g Ultraviolet absorber U-30,1g Ultraviolet absorber U-40,1g Ultraviolet absorber tJ-60,1g Additive P-10,1g Additive F-100,2g High Boiling point organic solvent 0i1-10.1g 2nd layer: Intermediate layer gelatin, 0.40g compound
Cpd-D 10mg Dye D-4
0.4mg High boiling point organic solvent 0il-340mg Dye D-60.1g 3rd layer: Interlayer non-photosensitive fine grain silver iodobromide emulsion (average grain size 0.1 μm, A
gI content 1 mol%) Silver amount 0.15 g Fine-grain silver iodobromide emulsion (average
Particle size 0.06μm, coefficient of variation 18%AgI content 1mol%
) Silver amount 0.05g Additive M-10.05g Gelatin 0.4g 4th layer: low
Sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.2g Emulsion 13
0.3g additive F-141m
g Gelatin 0.8g Compound Cp
d-K O, 05g coupler C-10
,15g Coupler C-20,05g Coupler C-90,05g Coupler C-100,1,0g Compound Cpd-D 10+ng added
Additive F2 0.1mg high boiling point organic solution
Medium 0il-20.10g Additive F-120.5mg 5th layer: medium-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2g Emulsion C Silver amount
0.3g Gelatin 0.8g Additive F-
13(), 05mg Coupler C-10,2g Coupler C-20,05g Coupler C-30,2g Additive F-20,1mg High-boiling organic solvent 0il-20,1g 6th layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4g gelatin
1.1g coupler C-30,7
g Coupler C-10,3g Additive P-10,1g Additive F-20,1a+g 7th layer: Intermediate layer gelatin 0.6g Color mixing inhibitor
Cpd-L 0.05g additive Fl
1.5ag additive F7
2. O+ag additive M-10.3g Color mixing prevention agent Cpd-K O.05g Ultraviolet light
Absorbent U-10.1g Ultraviolet absorber U-60.1g Dye D-10.02g Dye Dye 5 0.05g 8th layer:
Silver iodobromide emulsion (average grain size 0) covered with the surface and inside of the intermediate layer
．． 06 μm, coefficient of variation 16%, AgI content 0.3 mol%
) Silver amount 0.02g Gelatin 1.0g Additive P-
10.2g Color mixture prevention agent Cpd-J O,Ig color mixture prevention
Agent Cpd-M 0.05g Color mixing prevention agent Cp
d-A0.1g 9th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0, Iu
m, AgI content 0.1 mol%) Silver amount 0.05 g Emulsion E Silver amount 0.3 g Emulsion F
Silver amount 0.1g Emulsion G
Silver amount 0.1g gelatin
0.5g Coupler C-40, 20g Coupler C-70, lOg Coupler C-80, 10g Coupler C-110, 10g Compound Cpd-B O, 03g Compound
Cpd-E 0.02g Compound Cpd
-F 0.02g Compound Cpd-G
O,02g Compound Cpd-HO,02
g Compound Cpd-D 10g added
Additive F-50, 1 mg Additive F-30, 2 g Additive F-110, 51 g High boiling point organic solvent 0ff-20,2 g 10th layer: medium-sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount
0.1g gelatin 0.6g coupler C-
40.1g Coupler C-70.1g Coupler C-80.1g Coupler C-110.05g Compound Cpd-B O.03g Compound
Cpd-E 0.02g Compound Cpd
-F 0.02g Compound Cpd-G
O,05g Compound Cpd-80,05
g Additive F-50.08mg High boiling point organic solvent 0il-20.01g 11th layer: High sensitivity green sensitive emulsion layer Emulsion 1 Silver amount 0.5g Gelatin
1. Ig coupler C-40,4
g Coupler C-70,2g Coupler C-80,2g Coupler C-120,1g Coupler C-90,05g Compound Cpd-B O,08g Compound
Cpd-E 0.02g Compound Cpd
-F 0.02g Compound Cpd-G
O,02g Compound Cpd-H0,02
g Additive F-20.3 mg High boiling point organic solvent Oi 1-2 0.04 g Additive
F-130.05mg 12th layer: Intermediate layer gelatin 0.8g Additive F-1
2.0mg Additive F-8 2.0mg Dye D-10.1g Dye D-30.07g Dye D-80.03g Dye Dye 2 0.05g 13th layer
:Yellow filter layer Yellow colloidal silver Silver amount 0.1g gelatin
1.3g Dye D-50.05g Color mixing prevention agent Cpd-A O,O1g additive
F-40.3mg High boiling point organic solvent 0il-10.01g Dye Dye 7 0.03g Additive M
-20.01g 14th layer: Intermediate layer gelatin 0.6g Dye D-
9 0.02g] 5th layer: Low sensitivity
Blue sensitive emulsion layer Emulsion J Silver amount 0.4g Emulsion K
Silver amount 0.1g emulsion L
Silver amount 0.1g gelatin
0.9g Coupler C-130.1g Coupler C-50.6g Additive F-20.2mg Additive F-50.4rag Additive F-80.05mg 16th layer: Mid-speed blue-sensitive emulsion layer Emulsion L Silver amount 0.2g emulsion M
Silver amount 0.4g gelatin
1.2g Coupler C-130.1g Coupler C-50.3g Coupler C-60.3g Additive F-20.04mg Additive F-80.04mg 17th layer: High-speed blue-sensitive emulsion layer Emulsion N Silver amount 0 .4g gelatin
1.4g coupler C-60,5
g Coupler C-140.2g Additive F-20.4mg Additive F-80.02+ag Additive F-9111g 18th layer: 1st protective layer gelatin 0.9g UV absorption
Agent U-10,04g Ultraviolet absorber U-20,01g Ultraviolet absorber U-30,03g Ultraviolet absorber U-40,03g Ultraviolet absorber U-50,95g Ultraviolet absorber U-60,05g High boiling point organic solvent Oi 1-1 0.02g forma
Rinse Scavenger Cpd-C0, 2g Cpd-IO, 4g Latex dispersion of ethyl acrylate 0.05g Dye m-3
0.05g Additive F-11, Oa+g Additive F-70.5mg Additive M-20.05g 19th layer: 2nd protective layer colloidal silver Silver amount 0.1mg Insensitive Insensitive
Phototron silver iodobromide emulsion (average grain size 0.06 gm, AgI content 1 mol%) Silver amount 0.1 g Gelatin
0.7g 20th layer: 3rd protective layer gelatin 0.7g polymethyl
Methacrylate (average particle size 1.5μm)
0.1g methyl methacrylate and acrylic
4:6 acid copolymer (average particle size 1.5μm) 0.1g Silicone oil 0.03g Surfactant
Sex agent Wl 3.0+og surfactant W
-20.03g 21st layer (back layer) Gelatin 10g UV absorption
Absorbent U-10.05g Ultraviolet absorber U-20.02g High boiling point organic solvent 0il-10.01g 22nd layer (back protective layer) Gelatin 5g Polymethylene
methacrylate (average particle size 1.5 μm)
0.03g methyl methacrylate and acrylate
4:6 copolymer of lylic acid (average particle size 1.5 μm) 0.1 g Surfactant W-11B Surfactant W2 10 mg each halogen
Additive F-1 was added to the silver oxide emulsion. In addition to the above composition, each layer also contained gelatin hardening agent H-1.
and coating surfactants W-3 and W-4 for emulsification.
Surfactant W-5 was added. Furthermore, phenol 1,2-benz is used as a preservative and anti-mold agent.
Isothiazolin-3-one, 2-phenoxyethanol
, phenyl isothiocyanate, and phenethyl alcohol
was added. H I H C-4 (CHz-C)! CH2-CH)T
T average molecular weight: approx. 25,000 COOC3H? (iso)HC-12CH. `` Shireko 0i1-1 Dibutyl fuculate 0il-2 Tricresyl phosphate pd-A l CH pd-B pd-C pd-D CH pd-E Js 0 p d-F pd-G pd-H par-r CH. )II )III Cpd-J OH Cpd-K 0M Cpd-MO) 1 (J-1 Jn 503eON (C!Bs) 3 □ ChK bυkoNa OOH D ,,,,,,,,, 6 L)- 7 1',',',) --8 CtHs CzHsf(-1 CH,=CI(SO□CHzCONFICHzCHz=
CH5O2CHzCONHCHzCI. I C5F + tsOzN)I (CHz) 30 (C
Hz) zN-CHzC,F,7So□NCH,C00
K CJ'r CHzCOOCHzCH<CtHJC4HqNaJS-
CHCOOCHzCHCCtKs)CaHqP-'
-+CI1. -C1lh ■ CON+lC,1ll +CHz-C)l)- CC00C-H H HN02 F-5 The silver iodobromide whey used for sample 101 is as follows.
. Preparation of sample 102 Ultraviolet absorbers U-1 and U-2 in the 18th layer of sample 101
, except for removing U-3, U-4, U-5 and U-6.
Sample 102 was prepared in exactly the same manner as Sample 101. Preparation of samples 103 and 104 Fine grain silver iodobromide milk of the 19th layer of samples 101 and 102
Exactly the same as sample 101 and 102 except that the agent was removed.
Samples 103 and 104 were prepared. Preparation of Samples 105-108 A scarf of oxidized developing agent was added to the 18th layer of Samples 101-104.
CpdA, which is a bender, is applied in an amount of O, O1g/i.
Exactly the same as samples 101 to 104 except that
Samples 105 to 108 were prepared in this manner. Preparation of Samples 109 to 112 The 18th layer of Samples 102 to 104 and 101 was coated with the material of the present invention.
Compound (4) (average molecular weight: 3000) was added to sample 105~
The number of moles of CpdA and hydroquinone in 108 are the same.
Samples 102 to 104 and 101 and all
Samples 109 to 112 were prepared in the same manner. Preparation of samples 113 to 116 Instead of compound (4) in the 18th JIf of sample 112
, the compounds shown in Table 1 were combined with compound (4) and hydroquinone.
Completely similar to sample 112 except that the number of moles is the same.
Samples 113 to 116 were prepared in the same manner. These
The average molecular weight of all droquinone polymers is 3000.
there were. Preparation of samples 117 and 118 Yellow coupler in the 17th layer of samples 112 and 101
Sample 112 and
Samples 117 and 118 were prepared in exactly the same manner as 101.
. A large number of each of the samples 101 to 118 prepared in this way was
The following performance was compared. (1) First present
Kl dependence samples 101 to 118 in the image solution were passed through a light wedge.
The film was exposed to light and developed using Process A below. Samples 101 to 118 were exposed through a light wedge and subjected to the following treatment B.
It was developed and processed. Samples developed with processing A and processing B
Measures and processes the cyan, magenta, and yellow densities of
The logarithm of the exposure amount required for a density of 1.0 between A and processing B (ρo
gE) difference (ΔρogE) was determined. This △βogE
The smaller the value, the smaller the dependence on the amount of KI in the first developer.
Therefore, it can be said that it is preferable. The results are shown in Table 1. (2) Dmin (B) Samples 101 to 118 were exposed through a light wedge and subjected to the following treatment A.
Develop it with
and the minimum image density of yellow (Dakin (B)
) was sought. The present invention aims to reduce the value of D win (B).
It can be said that it is preferable for the purpose of The results are shown in Table 1.
. (3) Scratch-resistant samples 101 to 118 were straightened with a needle with a diameter of 0.5noo.
Scratch to. At this time, as you scratch in a straight line, the
Apply a load to the needle that causes a scratch, and measure the load that causes the scratch.
Set. It can be said that the larger the load, the better the wound resistance. There is no practical problem if the load is 100g or more (displayed as 0).
) If it is less than 100g, it will be a practical problem (x and
display). These results are shown in Table 1. (4) Color image stability (light brown) Samples 101 to 118 were exposed through a light wedge and treated with the following treatment A.
Develop it with
Established. These developed samples were exposed to xenon light for one week.
Cyan after continuous irradiation. Measure the density of magenta and yellow, and calculate each D f
Find the decrease in f1ax △D a+ax and use the result as the first
Shown in the table. (5) The treatment liquid contaminated sample 101 was exposed to light through a light wedge, and the following treatment A was applied to
Sample 101 corresponding to M was continuously developed. Sample 1
The first and last development process when developing 01 continuously
Measure the cyan, magenta, and yellow density of the sample.
No, the last processed sample is different from the first processed sample.
change in yellow sensitivity, yellow maximum image density (D
max) change (ΔDa+ax) was determined. Here, the change in sensitivity is the logarithm of the exposure amount required for a density of 1.0.
It was expressed as the difference (ΔβogE). Samples 102 to 118 were also treated in the same manner as sample 101.
△QogE and △D wax were calculated and the results are shown in Table 1.
. Processing A [Processing process] Black and white development 6 minutes 38°C 12β 2.2β/Golden water
Wash 2 minutes 38℃ 4ρ 7.5β/go inversion
2 minutes 38℃ 4℃ 1.1β/Go color development
6 minutes 38℃ 121 2.1/rrr adjustment
2 minutes 38℃ 4 β 1. II2/Go drifting
White 6 minutes 38℃ 12 g 0.21/g
Arrive 4 minutes 38℃ 8 I2 1. lρ/go
Second water wash 4 minutes 38℃ 8ρ 7.5I2. /Ian
Constant 1 minute 25℃ 2β 1.11/A various parts
The composition of the liquid was as follows. Saodan Gentaka mother liquor Replenisher Nitrilo-N,N,N- Trimethylenephosphonic acid pentasodium salt 2.0g 2.0g
Sodium sulfate 30g 30g
Hydroquinone/potassium monosulfonate 20g 20g charcoal
Potassium acid 33g 33g1
-Phenyl-4-methyl-4-hydroxyantyl-3-pyrazolidone 2.
Og 2.0g Potassium Bromide 2
．． 5g 1.4g Potassium thiocyanate 1
．． 2g 1.2g potassium iodide 2
．． 0mg - add water 1000
Acupuncture 1000100O, H9,609,60 pH was adjusted with hydrochloric acid or potassium hydroxide. Common nitrilo-N, N, N- trimethylenephosphonic acid pentasodium salt 3.0g First chloride
Tin dihydrate salt 1. Ogp-aminophe
Nol 0.1g Sodium hydroxide
8g glacial acetic acid
Add 15ml water 1
0001ipH6,00 pH was adjusted with hydrochloric acid or sodium hydroxide. xLJu liquid mother solution Replenisher Nitrilo-N,N,N- Trimethylenephosphonic acid pentasodium salt 2.0g 2.0g
Sodium sulfate 7.0g 7.0g
M3 Sodium Decahydrate 36g 36g Bromide
Potassium 1.0g - Potassium iodide
Lithium 90o+g - Sodium hydroxide
Rium 3.0g 3.0g Citrazine
Acid 1-5g 1.5g N-ethyl
-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g 11g3.
6-Sythia 1.8-Octanediol t,og 1.0g water
Add 1000n1 1000w
9X) H11,8012,00 pH was adjusted with hydrochloric acid or potassium hydroxide. l! Ethylenediaminetetraacetic acid, disodium salt, dihydrate salt 8.0g Sodium sulfite common to mother liquor/replenisher
Lium 12g1-thioglycerin
0.4ml sorbitan-ester*
O, add 1g water
1 (1 (10 pH 6,20 pH was adjusted with hydrochloric acid or sodium hydroxide. Ethanol mother liquor Replenisher Ethylene diamine 4 vinegar, Disodium salt, Dihydrate salt 2.t) g 4.0 g
Ethylenediaminetetraacetic acid, Fe(I[[), ammonium, dihydrate 120g 240g bromide
Potassium 100g 200g Nitric acid
Add ammonium log 20g water
1000m12 1000dp
H5,705,50 pH was adjusted with hydrochloric acid or sodium hydroxide. Ammonium thiosulfate common to L1 mother fluid/replenisher fluid 8.0g Sodium sulfite
Thorium 5.0g Sodium bisulfite
Add 5.0g water
1000ai! pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia. Xuanding base mother solution/replenisher common formalin (37% > 5.0 mpo)
Lyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5m! add water
Sorbitan ester without pH adjustment (w + x + y + z = = 20) Process B Increase the amount of potassium iodide in the first developer of Process A by 2.0 m
Exactly the same as treatment A except that g is reduced to 7.0 mg.
. From the results in Table 1, the following is clear. ■The protective layer contains a non-photosensitive fine-grain silver halide emulsion.
In this case, the change in sensitivity due to the amount of KI in the first developer is small.
(For example, from a comparison of samples 112 and 110). ■The protective layer must contain a non-photosensitive fine-grain silver halide emulsion.
If there is no hydroquinone compound in the protective layer, the yellow color
If D win is high and hydroquinone compounds are present, protection
to the same level as when there is no fine-grain silver halide emulsion in the layer.
(For example, sample 11
2 and 101). ■When the protective layer contains a monomer hydroquinone compound
, the scratch resistance deteriorates and becomes a practical problem. - The protective layer is exposed to heat.
Even if rokinone-based polymers are contained, there is almost no deterioration in scratch resistance.
(, there is no problem in practice (for example, samples 112 to 11)
6 and 105). ■If the protective layer contains an ultraviolet absorber, the color image becomes more stable against light.
Qualitativeness improves. However, the protective layer contains UV absorbers and monomers.
Containing a hydroquinone compound, UV absorber
The color image stabilizing effect of (for example, samples 112 to 11)
6 and 105). Hydroquinone compounding of monomers
If it contains a hydroquinone polymer instead of
The color image stabilizing effect of the line absorber is negligible. ■If the protective layer contains a monomer hydroquinone compound,
If the processing solution becomes contaminated and the amount of processing is increased, the photographic performance will change.
However, even if it contains a hydroquinone polymer,
There is almost no contamination of the processing solution (for example, samples 112 to 11)
6 and 105). Example 2 The color image stability test of Example I was performed using the adjustment of Process A of Example 1.
Exactly the same as Example 1 except that the liquid regulating and stabilizing liquids were changed to the following.
When this was carried out, substantially the same results as in Example 1 were obtained. 2. Mother solution/replenisher common solution
diaminetetraacetic acid, disodium salt, dihydrate 8.0g sodium sulfite
Lium 12g potassium carbonate
0.05 mol sorbitan ester*
Add 0.1g water 10
00 dpH8.50 pH was adjusted with hydrochloric acid or sodium hydroxide. Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5m1i!
Add water to 1000Tn[lp
Sorbitan ester without H adjustment (w + x + y + z = 20) Example 3 The color image stability test of Example 1 was carried out by adjusting the treatment A of Example 1.
Exactly the same as Example 1 except that the liquid regulating and stabilizing liquids were changed to the following.
When this was carried out, substantially the same results as in Example 1 were obtained. Place! Common solution/replenisher Ethylenediaminetetraacetic acid, disodium salt, dihydrate salt 8.0g Sodium sulfite
um 12.0g hexamethylenetetra
Min 3.5g2-Marcabuto-1,3,・4-triazole 0.5gTWEEN
20” Add 2.0 surimizu
1. OI2pH (25℃)
6.20 pH is adjusted with hydrochloric acid or sodium hydroxide.
I arranged it. TWEEN 20': ICI American
Inc., surfactant base solution mother liquor/replenisher common polyoxyethylene-p-monononylphenyl ether 0.2g ethylenedia
Minetetraacetic acid, disodium salt, dihydrate 1.0g stabilizer
Add 0.02g water
1.04pH (25℃)
7.00 pH was adjusted with acetic acid or aqueous ammonia
. zHOCHz-CH*-N, V/N -CH-CH2-O
H Example 4 Example 2, Sample 2 described in JP-A-2-90151
In 01, the test described in Example 1 of the present invention was carried out.
As a result, the same results as in Example 1 of the present invention were obtained.
. (Effect of the invention) The silver halide color photographic light-sensitive material of the present invention has a protective layer.
Increasing the Dmin of the adjacent photosensitive emulsion layer, improving scratch resistance and light resistance.
processing solution without deteriorating color image stability.
It is said that it is possible to suppress the pollution without being affected by it.
It has excellent effects.

Claims (1)

[Claims] A hydrophilic type having at least two photosensitive silver halide emulsion layers on a support, and at least one layer further from the support than the photosensitive silver halide emulsion layer located farthest from the support. In a silver halide color photographic light-sensitive material having a colloid layer (protective layer), at least one
The protective layer of the layer contains at least one emulsion selected from a non-photosensitive fine-grain silver halide emulsion and a fine-grain silver halide emulsion covered with grain surfaces and/or grain interiors, and at least one protective layer. A silver halide comprising at least one polymer or copolymer having a repeating unit containing a hydroquinone skeleton, and at least one protective layer containing at least one ultraviolet absorber. Color photographic material.